Presentation - National Water Research Institute
Presentation - National Water Research Institute
Presentation - National Water Research Institute
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Characterization of DOM in humic rich tributaries of a<br />
drinking water reservoir in Saxony using<br />
FTICR/MS and EEMF
Helmholtz Centre<br />
For Environmental <strong>Research</strong> – UFZ<br />
Peter Herzsprung, W. v. Tümpling, J. Bravidor<br />
(peter.herzsprung@ufz.de)<br />
Helmholtz Zentrum München<br />
German <strong>Research</strong> Centre for Environmental Health<br />
N. Hertkorn, M. Harir, P. Schmitt-Kopplin<br />
Characterization of DOM in humic rich tributaries of a<br />
drinking water reservoir in Saxony using<br />
FTICR/MS and EEMF
Problem: In Saxony drinking water is supplied<br />
from Ore Mountains reservoirs influenced<br />
by increasing DOC concentration of raw water
Problem: In Saxony drinking water is supplied<br />
from Ore Mountains reservoirs influenced<br />
by increasing DOC concentration of raw water<br />
Consequence:<br />
Usability of reservoir water as raw water can be limited by:<br />
- unpleasant taste, odour, and colour<br />
- increase of flocculation costs<br />
- undesirable harmful disinfection byproducts
Questions to be answered.<br />
1. What can be said about the relation between<br />
fluorescence and DOC?<br />
2. Is there any seasonal influence on the fluorescence<br />
DOC relation?<br />
3. What can be said about the abundance of typical<br />
compound groups?<br />
4. How can the information be used for using best<br />
raw drinking water?
water sampling<br />
DOC<br />
UV<br />
EEMF<br />
FTICR/MS<br />
bulk<br />
concentration<br />
bulk<br />
optical<br />
properties<br />
group<br />
species<br />
elemental<br />
formulae<br />
data analysis<br />
biogeochemical evaluation
water sampling<br />
DOC<br />
UV<br />
EEMF<br />
FTICR/MS<br />
bulk<br />
concentration<br />
bulk<br />
optical<br />
properties<br />
group<br />
species<br />
elemental<br />
formulae<br />
data analysis<br />
biogeochemical evaluation
Catchment area of reservoir Muldenberg<br />
Effluent TSP<br />
Saubach<br />
SBA<br />
Red Mulde<br />
RMU<br />
White Mulde<br />
WMU<br />
Sauteich<br />
STE<br />
Germany<br />
Saxony<br />
Muldenberg<br />
1 km<br />
W<br />
N<br />
S<br />
E
Reservoir<br />
Effluent<br />
Coloured water
water sampling<br />
DOC<br />
UV<br />
EEMF<br />
FTICR/MS<br />
bulk<br />
concentration<br />
bulk<br />
optical<br />
properties<br />
group<br />
species<br />
elemental<br />
formulae<br />
data analysis<br />
biogeochemical evaluation
water sampling<br />
DOC<br />
UV<br />
EEMF<br />
FTICR/MS<br />
bulk<br />
concentration<br />
bulk<br />
optical<br />
properties<br />
group<br />
species<br />
elemental<br />
formulae<br />
data analysis<br />
biogeochemical evaluation
methods<br />
2 0 0 0<br />
1 8 0 0<br />
1 6 0 0<br />
1 4 0 0<br />
1 2 0 0<br />
1 0 0 0<br />
8 0 0<br />
6 0 0<br />
4 0 0<br />
2 0 0<br />
0<br />
3D fluorescence (EEMF)<br />
2 4 0<br />
2 5 0<br />
2 6 0<br />
2 7 0<br />
2 8 0<br />
2 9 0<br />
3 0 0<br />
3 1 0<br />
3 2 0<br />
3 3 0<br />
3 4 0<br />
3 5 0<br />
3 6 0<br />
intensity<br />
(A.U.)<br />
emission 260 – 585 nm<br />
excitation<br />
240 – 360 nm
methods<br />
humic-like<br />
Ligninphenol<br />
like<br />
HO<br />
H<br />
C<br />
R<br />
?<br />
protein-like<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
0<br />
100<br />
200<br />
300<br />
400<br />
500<br />
Intensity<br />
(A.U.)<br />
HO<br />
OCH 3<br />
280<br />
According to Burdige et al,<br />
Marine Chem. 51, 325-346 (2004)<br />
260<br />
240<br />
Contour plot<br />
300 350 400 450 500 550<br />
Emission (nm)
methods<br />
Scaling of fluorescence diagrams<br />
Excitation (nm)<br />
Seite 14<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
Sampling site, date<br />
0<br />
200<br />
400<br />
600<br />
800<br />
Intensity (A.U.)<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
Median values<br />
Excitation:<br />
320 – 345 nm<br />
Emission:<br />
410 – 440 nm<br />
Wave length area<br />
for evaluation of<br />
fluorescence intensity<br />
(Humic like fluorescence)
water sampling<br />
DOC<br />
UV<br />
EEMF<br />
FTICR/MS<br />
bulk<br />
concentration<br />
bulk<br />
optical<br />
properties<br />
group<br />
species<br />
elemental<br />
formulae<br />
data analysis<br />
biogeochemical evaluation
OH<br />
O<br />
H<br />
H<br />
O<br />
C<br />
OH<br />
H<br />
H<br />
HOOC<br />
OH<br />
H<br />
O<br />
C<br />
C<br />
COOH<br />
H<br />
HO<br />
H<br />
H<br />
C 17 H 14 O 11 - millions of isomeric solutions?<br />
HO<br />
HO<br />
OH<br />
O<br />
OH<br />
H<br />
HO<br />
HO<br />
OH<br />
OH<br />
OH<br />
O C C<br />
H<br />
H<br />
H<br />
H
methods<br />
FTICR/MS elemental formulae <br />
van Krevelen diagrams: geochemical pools of DOM<br />
2,5<br />
2.5<br />
Simplified illustration<br />
H/C ratio<br />
2.0 2<br />
1.5 1,5<br />
1.0<br />
1<br />
0.5<br />
0,5<br />
lipids<br />
lignins<br />
black carbon<br />
proteins<br />
carbohydrates<br />
tannins<br />
0 0 0.2 0.4 0.6 0.8 1.0<br />
0 0,2 0,4 0,6 0,8 1<br />
O/C ratio
Questions to be answered.<br />
1. What can be said about the relation between<br />
fluorescence and DOC?<br />
2. Is there any seasonal influence on the fluorescence<br />
DOC relation?<br />
3. What can be said about the abundance of typical<br />
compound groups?<br />
4. How can the information be used for using best<br />
raw drinking water?
esults<br />
Humic like fluorescence versus DOC<br />
March July August<br />
RMU 0309<br />
RMU 0709<br />
RMU 0809<br />
RMU<br />
WMU<br />
excitation<br />
Excitation (nm)<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
360<br />
340<br />
320<br />
Excitation (nm)<br />
300<br />
440 A.U. 280<br />
622 A.U.<br />
WMU 0309<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
260<br />
240<br />
260<br />
0<br />
200<br />
400<br />
600<br />
800<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
11.7 mg/l 10.3 mg/l<br />
240<br />
300 350 400 450 500 550<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
WMU 0709<br />
300<br />
300<br />
435 A.U.<br />
280<br />
280 453 A.U.<br />
260<br />
240<br />
0<br />
200<br />
400<br />
600<br />
800<br />
9.1 mg/l<br />
300 350 400 450 500 550<br />
0<br />
200<br />
400<br />
600<br />
800<br />
Emission (nm)<br />
10.8 mg/l<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
360<br />
340<br />
320<br />
0<br />
200<br />
400<br />
600<br />
800<br />
8.2 mg/l<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
emission<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
0<br />
200<br />
400<br />
600<br />
800<br />
577 A.U.<br />
0<br />
200<br />
400<br />
600<br />
800<br />
Emission (nm)<br />
WMU 0809<br />
347 A.U.<br />
5.7 mg/l<br />
300 350 400 450 500 550<br />
Emission (nm)
Answer<br />
- No direct relation between the fluorescence<br />
and the DOC.<br />
- EEMF generates new information
Questions to be answered.<br />
1. What can be said about the relation between<br />
fluorescence and DOC?<br />
2. Is there any seasonal influence on the fluorescence<br />
DOC relation?<br />
3. What can be said about the abundance of typical<br />
compound groups?<br />
4. How can the information be used for using best<br />
raw drinking water?
esults Humic like fluorescence at different seasons<br />
excitation<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
January March April July August<br />
RMU 0109<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
Excitation (nm)<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
Emission (nm)<br />
WMU 0109<br />
360<br />
0<br />
200<br />
400<br />
340<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
SBA 0109<br />
360<br />
0<br />
200<br />
400<br />
340<br />
600<br />
800<br />
320<br />
300<br />
Excitation (nm)<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
STE 0109<br />
360<br />
0<br />
200<br />
400<br />
340<br />
600<br />
800<br />
320<br />
300<br />
Excitation (nm)<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
TSP 0109<br />
RMU 0309<br />
RMU 0409<br />
360<br />
0<br />
0<br />
200<br />
200<br />
400<br />
340 400<br />
600<br />
600<br />
800<br />
800<br />
320<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
300<br />
RMU<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
Emission (nm)<br />
WMU 0309<br />
WMU 0409<br />
360<br />
0<br />
0<br />
200<br />
200<br />
400<br />
340 400<br />
600<br />
600<br />
800<br />
800<br />
320<br />
300<br />
WMU<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
Emission (nm)<br />
SBA 0309<br />
SBA 0409<br />
360<br />
0<br />
0<br />
200<br />
200<br />
400<br />
340 400<br />
600<br />
600<br />
800<br />
800<br />
320<br />
300<br />
SBA<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
Emission (nm)<br />
STE 0309<br />
STE 0409<br />
360<br />
0<br />
0<br />
200<br />
200<br />
400<br />
340 400<br />
600<br />
600<br />
800<br />
800<br />
320<br />
300<br />
STE<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
Emission (nm)<br />
TSP 0309<br />
TSP 0409<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
RMU 0709<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
WMU 0709<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
SBA 0709<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
STE 0709<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
TSP 0709<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
RMU 0809<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
WMU 0809<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
SBA 0809<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
STE 0809<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
TSP 0809<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
Sept.<br />
RMU 0909<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
WMU 0909<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
SBA 0909<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
TSP 0909<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
October December<br />
RMU 1009<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
WMU 1009<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
SBA 1009<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
STE 1009<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
TSP 1009<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
RMU 1209<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
WMU 1209<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
SBA 1209<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
STE 1209<br />
360<br />
0<br />
200<br />
340 400<br />
600<br />
800<br />
320<br />
300<br />
280<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
TSP 1209<br />
pond tributaries<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
0<br />
200<br />
400<br />
600<br />
800<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
0<br />
200<br />
400<br />
600<br />
800<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
0<br />
200<br />
400<br />
600<br />
800<br />
TSP<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
360<br />
360<br />
0<br />
0<br />
200<br />
200<br />
400<br />
340 400<br />
340<br />
600<br />
600<br />
800<br />
800<br />
320<br />
320<br />
Excitation (nm)<br />
300<br />
300<br />
280<br />
280<br />
260<br />
260<br />
240<br />
240<br />
300 350 400 450 500 550<br />
300 350 400 450 500 550<br />
emission<br />
Emission (nm)<br />
Emission (nm)<br />
Excitation (nm)<br />
0<br />
200<br />
400<br />
600<br />
800<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
0<br />
200<br />
400<br />
600<br />
800<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
0<br />
200<br />
400<br />
600<br />
800<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
effluent
esults<br />
Seasonal behaviour of DOC and fluorescence<br />
Quotient of<br />
median fluorescence intensity<br />
and DOC<br />
Seite 23
Answer<br />
- Specific fluorescence activity (of DOC) rise<br />
between March and September.<br />
- Specific fluorescence activity rise can not be explained<br />
by EEMF.
Question to be answered.<br />
1. What can be said about the relation between<br />
fluorescence and DOC?<br />
2. Is there any seasonal influence on the behaviour?<br />
3. What can be said about the abundance of typical<br />
compound groups?<br />
- seasonal effect<br />
- relation between fluorescence and<br />
biogeochemical pools<br />
4. How can the information be used for using best<br />
raw drinking water?
esults<br />
FTICR/MS data available<br />
Quotient of<br />
median fluorescence intensity<br />
and DOC<br />
Seite 26
esults<br />
Bulk van Krevelen diagrams<br />
2<br />
1.5<br />
1<br />
0.5<br />
0<br />
black carbon<br />
H/C<br />
O/C<br />
1<br />
lipids<br />
March<br />
0 0.2 0.4 0.6 0.8 1<br />
2<br />
1.5<br />
proteins carbohydrates<br />
lignins<br />
tannins<br />
Evaluation of CHO formulae;<br />
CHOS and CHON not considered<br />
0.5<br />
0<br />
July<br />
0 0.2 0.4 0.6 0.8 1
esults<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
2<br />
0<br />
200<br />
400<br />
600<br />
800<br />
DOC<br />
RMU3<br />
RMU 0309<br />
Difference in abundance of elemental formulae<br />
Excitation (nm)<br />
RMU 0709<br />
280<br />
260<br />
9.1 mg/l 11.7 mg/l<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
360<br />
340<br />
320<br />
300<br />
240<br />
0<br />
200<br />
400<br />
600<br />
800<br />
DOC<br />
RMU7<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
RMU3 + RMU7<br />
2<br />
1.5<br />
1<br />
0.5<br />
0<br />
2<br />
RMU3<br />
different abundance<br />
0 0.2 0.4 0.6 0.8 1<br />
RMU7<br />
1.5<br />
1.5<br />
1<br />
0.5<br />
0<br />
common abundance<br />
H/C<br />
0 0.2 0.4 0.6 0.8 1<br />
1<br />
0.5<br />
O/C<br />
0<br />
different abundance<br />
0 0.2 0.4 0.6 0.8 1
esults<br />
mass peaks<br />
biunique<br />
assignment<br />
intensity values<br />
Rank analysis (different seasons) FTICR/MS<br />
for 638 common elemental formulae in 4 samples<br />
C 17 H 14 O 11<br />
rank within<br />
638 el.<br />
formulas<br />
rank within<br />
4 samples<br />
RMU3 124 4<br />
March<br />
RMU4 86 3<br />
April<br />
RMU7 36 1<br />
July<br />
RMU8 52 2<br />
August
esults<br />
mass peaks<br />
Rank analysis (different seasons) FTICR/MS<br />
for 638 common elemental formulae in 4 samples<br />
2.5<br />
biunique<br />
assignment<br />
C 17 H 14 O 11<br />
rank within<br />
638 el.<br />
formulas<br />
rank within<br />
4 samples<br />
RMU3 124 4<br />
March<br />
RMU4 86 3<br />
April<br />
RMU7 36 1<br />
July<br />
RMU8 52 2<br />
August<br />
intensity values<br />
0 1<br />
Van Krevelen diagrams<br />
2<br />
1.5<br />
1<br />
0.5<br />
H/C<br />
0<br />
O/C<br />
0<br />
Rank 1<br />
Rank 2<br />
Rank 3<br />
Rank 4<br />
Red Mulde / July<br />
depiction of the ranked formulae<br />
0 0.2 0.4 0.6 0.8 1
esults<br />
2<br />
1.5<br />
1<br />
Rank analysis (different seasons) FTICR/MS<br />
Red Mulde<br />
2.5<br />
0<br />
Rank 1<br />
Rank 2<br />
Rank 3<br />
Rank 4<br />
0 1<br />
lignins<br />
tannins<br />
0.5<br />
0<br />
March<br />
H/C<br />
O/C<br />
0 0.2 0.4 0.6 0.8 1<br />
2<br />
1.5<br />
Red Mulde<br />
1<br />
0.5<br />
0<br />
July<br />
0 0.2 0.4 0.6 0.8 1
esults<br />
2<br />
1.5<br />
1<br />
Rank analysis (different seasons) FTICR/MS<br />
Red Mulde<br />
2.5<br />
0<br />
Rank 1<br />
Rank 2<br />
Rank 3<br />
Rank 4<br />
0 1<br />
lignins<br />
tannins<br />
0.5<br />
0<br />
March<br />
H/C<br />
O/C<br />
0 0.2 0.4 0.6 0.8 1<br />
2<br />
1.5<br />
Red Mulde<br />
1<br />
0.5<br />
0<br />
July<br />
0 0.2 0.4 0.6 0.8 1
esults<br />
2<br />
1.5<br />
1<br />
Rank analysis (different seasons) FTICR/MS<br />
Saubach<br />
2.5<br />
0<br />
Rank 1<br />
Rank 2<br />
Rank 3<br />
Rank 4<br />
0 1<br />
lignins<br />
tannins<br />
0.5<br />
0<br />
March<br />
H/C<br />
O/C<br />
0 0.2 0.4 0.6 0.8 1<br />
2<br />
1.5<br />
Saubach<br />
1<br />
0.5<br />
0<br />
July<br />
0 0.2 0.4 0.6 0.8 1
Question to be answered.<br />
1. What can be said about the relation between<br />
fluorescence and DOC?<br />
2. Is there any seasonal influence on the behaviour?<br />
3. What can be said about the abundance of typical<br />
compound groups?<br />
- seasonal effect<br />
- relation between fluorescence and<br />
biogeochemical pools<br />
4. How can the information be used for using best<br />
raw drinking water?
Flößgrabenquelle<br />
Red Mulde<br />
Black<br />
pool<br />
DOC 0.37 mg/l<br />
DOC 10.3 mg/l<br />
DOC 83 mg/l<br />
2<br />
2<br />
2<br />
1.5<br />
1.5<br />
1.5<br />
H/C<br />
1<br />
H/C<br />
1<br />
H/C<br />
1<br />
0.5<br />
0<br />
0 0.2 0.4 0.6 0.8 1<br />
Pr4 SBA 0809 O/CFlöss Q unten<br />
0.5<br />
0<br />
0 0.2 0.4 0.6 0.8 1<br />
O/C RMU 0809<br />
0.5<br />
0<br />
1:5 diluted<br />
0 0.2 0.4 0.6 0.8 1<br />
O/C<br />
Rote Mulde Pr11<br />
excitation<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
0<br />
200<br />
400<br />
600<br />
800<br />
300 350 400 450 500 550<br />
emission<br />
Emission (nm)<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
0<br />
200<br />
400<br />
600<br />
800<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
0<br />
200<br />
400<br />
600<br />
800<br />
undiluted<br />
300 350 400 450 500 550<br />
Emission (nm)
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
0<br />
200<br />
400<br />
600<br />
800<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0<br />
200<br />
400<br />
600<br />
800<br />
300 350 400 450 500 550<br />
0<br />
200<br />
400<br />
600<br />
800<br />
0<br />
200<br />
400<br />
600<br />
800<br />
Emission (nm)<br />
300 350 400 450 500 550<br />
0<br />
200<br />
400<br />
600<br />
800<br />
Emission (nm)<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
results<br />
EEMF<br />
Comparison between fluorescence ranking<br />
and mass intensity inter samples ranking<br />
Sample EEMF FTICR/MS-Ranks (455 common compounds)<br />
Nr Name Ranks C 17 H 14 O 11 C 20 H 28 O 7<br />
Comp. …<br />
RMU 0709<br />
3<br />
Comp.<br />
455<br />
1 RMU7 1 1 17 … … …<br />
… WMU7 3 2 14 … … …<br />
… TSP7 8 10 16 … … …<br />
… STE7 15 15 19 … … …<br />
… SBA7 18 19 11 … … …<br />
… … … … … … … …<br />
20 … … … … … … …<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
WMU 0709<br />
TSP 0709<br />
STE 0709<br />
SBA 0709<br />
Rank correlation<br />
(Spearman)<br />
FTICR/MS<br />
for each compound
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
0<br />
200<br />
400<br />
600<br />
800<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0<br />
200<br />
400<br />
600<br />
800<br />
300 350 400 450 500 550<br />
0<br />
200<br />
400<br />
600<br />
800<br />
0<br />
200<br />
400<br />
600<br />
800<br />
Emission (nm)<br />
300 350 400 450 500 550<br />
0<br />
200<br />
400<br />
600<br />
800<br />
Emission (nm)<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
results<br />
EEMF<br />
Comparison between fluorescence ranking<br />
and mass intensity inter samples ranking<br />
Sample EEMF FTICR/MS-Ranks (455 common compounds)<br />
Nr Name Ranks C 17 H 14 O 11 C 20 H 28 O 7<br />
Comp. …<br />
RMU 0709<br />
3<br />
Comp.<br />
455<br />
1 RMU7 1 1 17 … … …<br />
… WMU7 3 2 14 … … …<br />
… TSP7 8 10 16 … … …<br />
… STE7 15 15 19 … … …<br />
… SBA7 18 19 11 … … …<br />
… … … … … … … …<br />
20 … … … … … … …<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
Excitation (nm)<br />
WMU 0709<br />
TSP 0709<br />
STE 0709<br />
SBA 0709<br />
Rank correlation<br />
(Spearman)<br />
Level of significance 0.001 non sign.<br />
FTICR/MS<br />
for each compound
esults<br />
H/C<br />
2<br />
1.5<br />
1<br />
0.5<br />
Elemental formulae and their corresponding levels of<br />
xxxsignificance for correlation with humic like fluorescence<br />
Level of significance<br />
for rank correlation<br />
0.001<br />
0.005<br />
0.01<br />
0.025<br />
0.05<br />
0.1<br />
non sig.<br />
C 20 H 28 O 7<br />
C 17 H 14 O 11<br />
0<br />
0 0.2 0.4 0.6 0.8 1<br />
O/C
Answers<br />
Typical compound groups:<br />
- No or minor proteins, carbohydrates, and lipids<br />
- Dominant lignins and tannins<br />
Seasonal behaviour<br />
- Elevated input of tannins during summer months,<br />
mainly in Red Mulde and White Mulde<br />
- Opposite behaviour of the Saubach<br />
Relation of fluorescence – compound groups<br />
- The origin of humic like fluorescence (in this area)<br />
can be allocated within the pool of tannic acids
Question to be answered.<br />
1. What can be said about the relation between<br />
fluorescence and DOC?<br />
2. Is there any seasonal influence on the behaviour?<br />
3. What can be said about the abundance of typical<br />
compound groups?<br />
4. How can the information be used for using best<br />
raw drinking water?
As an example: citation from the U.S. Geolical Survey<br />
tannins are more reactive with chlorine to produce<br />
undesirable disinfection by-products than are terpenoids<br />
the abundance of tannins correlates with humic like<br />
fluorescence<br />
low<br />
Raw water<br />
is appropriate<br />
Fluoresc./DOC<br />
quotient<br />
+<br />
DOC<br />
?<br />
quality<br />
quantity<br />
high<br />
tannins<br />
Raw water<br />
is unsuitable<br />
Drinking water abstraction
4. How can the information be used for using best raw drinking<br />
water?<br />
clear decision<br />
better quality<br />
worse quality<br />
?
Conclusion<br />
• In our study area tannins could be identified as an<br />
ximportant biogeochemical pool within the DOC cycle of<br />
xthe surface water<br />
• The inter samples ranking analysis is the key to connect<br />
xoptical properties of DOM with geochemical pools derived<br />
xfrom FTICR/MS<br />
• The humic like fluorescence is an easy and low cost<br />
xadditional criterion for raw water quality evaluation
Visions:<br />
• Investigation of different fluorescent compounds using<br />
xPARAFAC (statistical fluorescence analysis)<br />
• Correlation of fluorescence compounds derived from<br />
xPARAFAC with geochemical pools derived from van<br />
xKrevelen diagrams<br />
• Correlation of fluorescent compounds and elemental<br />
xformulae compounds with disinfection byproducts<br />
xformation potential or flocculation costs
0.51 1.52 2.50<br />
01<br />
2.5 2,5<br />
2.0 2<br />
1.5 1,5<br />
1.0 1<br />
0.5 0,5<br />
0<br />
0 0,2 0,4 0,6 0,8 1<br />
0,51 1,52 2,50<br />
0<br />
Opportunity to visit me at the posters<br />
NOM characterisation in highly acidic iron rich pore waters of<br />
mine pit lakes using ultra high – resolution mass spectrometry<br />
Peter Herzsprung 1 , Norbert Hertkorn 2 ,MouradHarir 2 , Kurt Friese 1 , Philippe Schmitt-Kopplin 2<br />
1 UFZ Centre for Environmental <strong>Research</strong> Leipzig-Halle, Department Lake <strong>Research</strong>, Brückstr. 3a, 39114 Magdeburg, Germany<br />
2 HelmholtzZentrum München, German <strong>Research</strong> Center for Environment and Health, <strong>Institute</strong> of Ecological Chemistry, Ingolstädter Landstrasse 1, 85764 Neuherberg, Germany<br />
Contact: samples & ecology; elemental formula evaluation: peter.herzsprung@ufz.de, FTICR/MS: schmitt-kopplin@helmholtz-muenchen.de<br />
Introduction<br />
Analysis of DOM<br />
The leakage of acidic mine drainage from abandoned mine tailings and High-resolution spectra were acquired (in the negative ion<br />
overburden dumps, as a result of chemical and microbial oxidation of sulphide mode) with a APEX Qe FTICR mass spectrometer (Bruker,<br />
minerals is of major environmental concern. While chemical parameters such Bremen, Germany) equipped with a 12 TESLA superconducting<br />
as the amount of dissolved inorganic ions and the concentration of bulk magnet and an Apollo II microelectrospray source. FTICR mass<br />
dissolved organic carbon (DOC) can be accurately determined, understanding spectral peaks with a signal-to-noise ratio (S/N) > 2 were<br />
of the molecular composition of DOM in such acidic iron-rich environments exported to peak lists. Feasable elemental formulae (C≤100,<br />
remains incomplete. The exceptional complexity of DOM requires highresolution<br />
structural spectroscopy such as electrospray ionisation (ESI) validation). The procedure for extraction of reliable formulae<br />
O≤80, N≤5, S≤1) were computed for each peak (after 13 C<br />
Fourier transform ion cyclotron resonance mass spectrometry (FTICR/MS).<br />
from the data set is described by Herzsrung et al. [1].<br />
Differences in DOM quality abundance of elemental formulae<br />
Lake 111 (2007) Lake Moritzteich (2007)<br />
Lake Waldsee (2007)<br />
Mixolimnion pH 2.6 + Monimolimnion pH 6.8<br />
Monimolimnion pH 6.6<br />
Mixolimnion pH 3.1<br />
Mixolimnion pH 7.0<br />
H/C<br />
0.5<br />
pore-water pH Fe SO 2-<br />
4<br />
DOC<br />
0 - 2.5 cm<br />
Lake 111 2.6 80 mg/l 1060 mg/l 19 mg/l<br />
Lake Moritzteich 6.8 450 mg/l 330 mg/l 220 mg/l<br />
acidic pore water neutral pore water<br />
0<br />
0 0.2 0.4 0.6 0.8 1<br />
O/C<br />
Further differentiation of elemental formulae with common abundance<br />
inter samples ranking analysis of mass intensities<br />
example pH rank within rank within<br />
C 15 H 12 O 9 420 comp. 7 samples<br />
0 – 2 cm 2.8 278 7<br />
2 – 4 cm 3.0 220 5<br />
4 – 6 cm 2.9 221 6<br />
6 – 8 cm 3.0 205 4<br />
10 – 15 cm 3.0 80 3<br />
15 – 20 cm 3.2 71 2<br />
> 20 cm 3.2 35 1<br />
Conclusions<br />
Differences in DOM quality can be demonstrated:<br />
exemplified:<br />
by C x H y O z S 1 and C x H y O z N 1 compounds for different lakes<br />
and 2 different sediment depths respectively<br />
by C x H y O z compounds for 7 sediment depths<br />
by C x H y O z compounds for pore waters from 4 different lakes<br />
• by different abundance diagrams<br />
• by ranking analysis of formulae with<br />
xcommon abundance<br />
• in pore waters from different lakes<br />
• as a function of sediment depth<br />
H/C<br />
2.5<br />
2<br />
C x y x H y O z z<br />
Lake 111 (2009)<br />
0-2 cm<br />
1.5<br />
2-4 cm<br />
4-6 cm<br />
6-8 cm<br />
1<br />
10-15 cm<br />
15-20 cm<br />
0.5<br />
> 20 cm<br />
rank 1<br />
C15H12O9 C 12O 9<br />
0<br />
0 0.2 0.4 0.6 0.8 1<br />
O/C<br />
Trends can be observed:<br />
Lake Waldsee pH Fe SO 2-<br />
4 DOC<br />
pore-water 0 - 2.5 cm 6.7 94 mg/l 68 mg/l 71 mg/l<br />
pore-water > 20 cm 12 < 1 mg/l < 20 mg/l 29 mg/l<br />
2.5<br />
2.5<br />
2.5<br />
C common abundance<br />
common abundance<br />
x H y O z S 1 C x H y O z S 1<br />
C x H y O z N 1<br />
acidic<br />
2<br />
2<br />
2<br />
alkaline<br />
1.5<br />
1.5<br />
1.5<br />
neutral<br />
1<br />
different<br />
1<br />
1<br />
abundance<br />
H/C<br />
0.5<br />
Neutral iron rich pore waters seem to contain<br />
more aromatic and oxygen rich NOM whereas<br />
acidic or even alkaline pore waters are<br />
dominated by more aliphatic and oxygen poor<br />
compounds<br />
H/C<br />
alkaline pore water neutral pore water<br />
0<br />
0 0.2 0.4 0.6 0.8 1<br />
O/C<br />
H/C<br />
2.5<br />
0.5<br />
alkaline pore water neutral pore water<br />
0<br />
0 0.2 0.4 0.6 0.8 1<br />
O/C<br />
Different pore waters<br />
> 20 cm sediment depth (2007)<br />
C x H y O z<br />
References:<br />
common abundance<br />
2<br />
Lake 111<br />
pH 3<br />
1.5<br />
Waldsee<br />
pH 12<br />
1<br />
Moritzteich<br />
pH 6.5<br />
0.5<br />
Lake<br />
rank 1<br />
Goitsche<br />
pH 5.8<br />
0<br />
0 0.2 0.4 0.6 0.8 1<br />
O/C<br />
[1] Herzsprung, P. et al. (2010)<br />
Rapid. Commun. Mass Spectrom. 24,<br />
2909-2924<br />
Photochemical degradation of NOM compounds – itemisation<br />
by single elemental formula evaluation received from ultrahigh-resolution<br />
mass spectrometry<br />
1.5<br />
H/C<br />
1<br />
2.5<br />
0.5<br />
1. Samples from acidic<br />
pit lake pore-waters<br />
Artificial experiment<br />
Sediment<br />
Fe 3+ solution<br />
pore-water<br />
pH 2.3<br />
rich in DOC and Fe 2+<br />
contains no Fe 3+<br />
Sunlight<br />
Artificial solution<br />
2<br />
1.5<br />
H/C<br />
1<br />
Dark<br />
Br control<br />
C x H y O z<br />
0<br />
0 0.2 0.4 0.6 0.8ND<br />
1<br />
O/C<br />
PD<br />
Lake Moritzteich<br />
MinP<br />
pore water (20 – 30 cm)<br />
TD<br />
NewP<br />
2.5<br />
2<br />
0.5<br />
FTICR / MS<br />
Irradiated<br />
sample Q<br />
Comparison of educts and<br />
products formula by formula<br />
Q = Quartz glass<br />
Br = Brown glass<br />
Data mining<br />
C x H y O z S 1<br />
0<br />
0 0.2 0.4 0.6 0.8 1<br />
O/C<br />
Examination of<br />
degradation status<br />
Peter Herzsprung 1a , Wolf von Tümpling 1b , Norbert Hertkorn 2 , Mourad Harir 2 , Kurt Friese 1a , Philippe Schmitt-Kopplin 2<br />
1 UFZ Centre for Environmental <strong>Research</strong> Leipzig-Halle, Department a Lake <strong>Research</strong> / b River Ecology, Brückstr. 3a, 39114 Magdeburg, Germany<br />
2 HelmholtzZentrum München, German <strong>Research</strong> Center for Environment and Health, <strong>Institute</strong> of Ecological Chemistry, Ingolstädter Landstrasse 1, 85764 Neuherberg, Germany<br />
Contact: samples & ecology; elemental formula evaluation: peter.herzsprung@ufz.de, ICR-FT/MS: schmitt-kopplin@helmholtz-muenchen.de<br />
Introduction<br />
Analysis of DOM<br />
Sunlight-induced photooxidation is an important removal pathway for DOM. ESI-<br />
High-resolution spectra were acquired (in the negative ion<br />
FTICR/MS as an high end analytical method becomes more and more important<br />
mode) with a APEX Qe FTICR mass spectrometer (Bruker,<br />
to explain sunlight-induced degradation processes [1,2]. For the assessment of<br />
Bremen, Germany) equipped with a 12 TESLA superconducting<br />
magnet and an Apollo II microelectrospray<br />
photochemical changes in DOM a comparison of mass reactants and products,<br />
which were received from FTICR/MS data tables, can be done formula by<br />
source. FTICR mass spectral peaks with a signal-to-noise<br />
formula [1,3]. In a rather simplified experiment, two different types of samples<br />
ratio (S/N) > 2 were exported to peak lists. Feasable<br />
(1. from acidic pit lake pore waters; 2. from a drinking water reservoir tributary)<br />
elemental formulae (C≤100, O≤80, N≤5, S≤1) were computed<br />
were exposed to sunlight. The spectra of the reactants were derived from<br />
for each peak (after 13 C validation). The procedure for<br />
measured dark control (brown glass flask) and the spectra of the products were<br />
extraction of reliable formulae from the data set is<br />
derived from investigated solution in the quartz glass flasks.<br />
described by Herzsrung et al. [3].<br />
Degradation<br />
mass<br />
Sample Calculated<br />
(Da)<br />
ND<br />
ND<br />
NewP<br />
TD<br />
PD<br />
PD<br />
MinP<br />
MinP<br />
H/C ratio<br />
Br<br />
Q<br />
Q<br />
Br<br />
Br<br />
Q<br />
Br<br />
Q<br />
Mass<br />
intensity<br />
206.130680 3487448 18 13 2<br />
206.130680 2700959 18 13 2<br />
207.053159 12215212 9 10 4<br />
207.071785 347281 13 11 1<br />
208.019416 7829639 8 10 3<br />
208.019416 2483020 8 10 3<br />
208.037175 11848488 8 10 5<br />
208.037175 177581290 8 10 5<br />
H<br />
C<br />
O N S<br />
ND: 50% (Br) < Int. (Q) < 200% (Br)<br />
not significantly degraded<br />
PD: Int. (Q) < 50% (Br)<br />
partially degraded<br />
MinP: Int. (Q) > 200% (Br)<br />
minor new photoproduct<br />
TD: Not found in Q, found in Br<br />
totally degraded<br />
NewP: Found in Q, not found in Br<br />
newly formed photoproduct<br />
Allocation of<br />
geochemical pools in<br />
van Krevelen diagrams<br />
Simplified illustration<br />
lipids proteins carbohydrates<br />
lignins<br />
tannins<br />
black carbon<br />
0<br />
0 0.2 0.4 0.6 0.8 1.0<br />
O/C ratio<br />
References:<br />
[1] Gonsior, M. et al. (2009)<br />
Environ. Sci. Technol. 43,<br />
698-703<br />
[2] Kujawinski, E.B. et al. (2004)<br />
Mar. Chem. 92, 23-37<br />
[3] Herzsprung, P. et al. (2010)<br />
Rapid. Commun. Mass Spectrom. 24,<br />
2909-2924<br />
0 0<br />
0 0<br />
1 0<br />
1 1<br />
0 1<br />
0 1<br />
0 0<br />
0 0<br />
2.5<br />
2<br />
1.5<br />
H/C<br />
1<br />
0.5<br />
2. Sample from a drinking<br />
water reservoir tributary<br />
Dark<br />
Br control<br />
Sample<br />
FTICR / MS<br />
Irradiated<br />
sample Q<br />
Comparison of educts and<br />
products formula by formula<br />
C x H y O z<br />
Sunlight<br />
Q = Quartz glass<br />
Br = Brown glass<br />
Data mining<br />
0<br />
0 0.2 0.4 0.6 0.8 1<br />
O/C<br />
Conclusions<br />
Color coded van Krevelen diagrams<br />
differentiation of the photo degradation behaviour of NOM<br />
xxxis possible<br />
Drinking water reservoir tributary<br />
< 10% DOC mineralisation<br />
total degradation mainly of tannic acid like compounds<br />
C x H y O z S 1 not relevant compared to C x H y O z<br />
ND<br />
PD<br />
MinP<br />
TD<br />
NewP<br />
Pore waters from acidic mine pits (+ ferric iron)<br />
> 40% DOC mineralisation on average<br />
degradation of compounds from different geochemical<br />
xxxpools<br />
Higher degradation rate of C x H y O z S 1 compared to C x H y O z
2 0 0 0<br />
1 8 0 0<br />
1 6 0 0<br />
1 4 0 0<br />
1 2 0 0<br />
1 0 0 0<br />
8 0 0<br />
6 0 0<br />
4 0 0<br />
2 0 0<br />
0<br />
2 4 0<br />
2 5 0<br />
2 6 0<br />
2 7 0<br />
2 8 0<br />
2 9 0<br />
3 0 0<br />
3 1 0<br />
3 2 0<br />
3 3 0<br />
3 4 0<br />
3 5 0<br />
3 6 0<br />
Thank you for your attention<br />
2<br />
1.5<br />
1<br />
0.5<br />
0<br />
0 0.2 0.4 0.6 0.8 1<br />
Questions?
Discussion
Discussion<br />
Fluo-Imager M153<br />
Used in the<br />
laboratory<br />
Excitation: 240 – 360 nm<br />
Emission: 260 – 575 nm
Discussion<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
irradiated sample<br />
irradiated sample (mean)<br />
0<br />
200<br />
400<br />
600<br />
800<br />
Red Mulde<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
dark control<br />
0<br />
200<br />
400<br />
600<br />
800<br />
dark control (mean)<br />
260<br />
9.1 mg/l DOC 260<br />
9.7 mg/l DOC<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
dark control - irradiated sample<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
dark control - irradiated sample<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0<br />
10<br />
20<br />
30<br />
40<br />
50<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0<br />
50<br />
100<br />
150<br />
200<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
relative<br />
difference [%]<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
absolute<br />
difference
Discussion
Discussion<br />
MacDonald, B.C., Lvin, S.J., Patterson, H.: Correction of fluorescence<br />
inner filter effects and the partitioning of pyrene to<br />
dissolved organic carbon. Anal. Chim. Acta 338, 155-162 (1997).
Discussion<br />
Intensity<br />
(humic like fluorescence)<br />
Median values<br />
Excitation:<br />
320 – 345 nm<br />
Emission:<br />
410 – 440 nm<br />
700<br />
600<br />
500<br />
400<br />
300<br />
200<br />
100<br />
0<br />
Humic like fluorescence at different seasons<br />
SBA<br />
RMU8<br />
STE<br />
WMU<br />
WMU7<br />
RMU WMU8<br />
TSP<br />
RMU3<br />
RMU1<br />
SBA1<br />
RMU4<br />
WMU4<br />
0 2 4 6 8 10 12 14<br />
DOC mg/l<br />
RMU7<br />
WMU3<br />
1= January<br />
3= March<br />
4= April<br />
7= July<br />
8= August
Discussion<br />
0,6<br />
RMU7<br />
0,5<br />
WMU3<br />
0,4<br />
RMU3<br />
WMU7<br />
RMU8<br />
SBA<br />
UV254<br />
0,3<br />
STE3<br />
SBA3<br />
TSP3<br />
TSP4<br />
STE<br />
WMU<br />
RMU<br />
TSP<br />
0,2<br />
0,1<br />
SBA8<br />
SBA7<br />
WMU8<br />
TSP7<br />
STE7<br />
RMU4<br />
WMU4<br />
TSP8<br />
STE8<br />
Alle<br />
Linear (Alle)<br />
STE4<br />
SBA4<br />
0<br />
0 2 4 6 8 10 12 14<br />
DOC mg/l
Discussion<br />
700<br />
RMU7<br />
600<br />
RMU8<br />
fluorescence intensity<br />
500<br />
400<br />
300<br />
200<br />
STE4<br />
TSP8<br />
STE8<br />
RMU4<br />
WMU4<br />
SBA7<br />
WMU7<br />
TSP4<br />
TSP7<br />
TSP3<br />
WMU8<br />
STE7 STE3<br />
SBA3<br />
RMU3<br />
WMU3<br />
SBA<br />
STE<br />
WMU<br />
RMU<br />
TSP<br />
Alle<br />
Polynomisch (Alle)<br />
100<br />
SBA4<br />
SBA8<br />
0<br />
0 0,1 0,2 0,3 0,4 0,5 0,6<br />
UV 254nm
Discussion<br />
Evaluation of spectra by PARAFAC<br />
Used: 52 Spectra, 11 sampling sites in 2009<br />
PARAFAC = parallele faktor analysis<br />
• based on a 3D-Matrix<br />
X<br />
( Ix JxK)<br />
I<br />
J<br />
K<br />
with<br />
I … sample<br />
J … excitation wave lengths<br />
K … emission wave lengths<br />
• aim: minimisation of error square sum<br />
• algorithm: alternating least squares (ALS)<br />
result: PARAFAC-model with 5 fluorescent compounds
Discussion<br />
evaluation of spectra by PARAFAC<br />
result: PARAFAC-model with 5 fluorescent compounds<br />
Compound 3<br />
Compound 1<br />
Compound 2<br />
Compound 4 Compound 5
intensity<br />
25<br />
20<br />
15<br />
10<br />
5<br />
0<br />
sample 1 sample 2<br />
sample 3<br />
f 1 f 2 f 3 f 4 f 5<br />
rank value<br />
6<br />
5<br />
4<br />
3<br />
2<br />
1<br />
0<br />
f 1 f 2 f 3 f 4 f 5<br />
scaling by<br />
rank calculation<br />
rank value =<br />
= 1 + number of formulae - rank<br />
rank of<br />
formula 1<br />
formula 2<br />
formula 3<br />
formula 4<br />
formula 5<br />
rank<br />
6<br />
5<br />
4<br />
3<br />
2<br />
1<br />
0<br />
f 1 f 2 f 3 f 4 f 5<br />
Discussion
ank value<br />
10<br />
8<br />
6<br />
4<br />
2<br />
0<br />
sample 1 sample 2 sample 3 sample 4 sample 5<br />
f 1 f 2 f 3 f 4 f 5 f 6 f 7 f 8<br />
Discussion<br />
Rank calculation between<br />
samples considering the<br />
specific rank values for<br />
all formulae which are<br />
abundant in each sample<br />
sample rank compound<br />
1 4 m1=300<br />
2 1 m1=300<br />
3 5 m1=300<br />
4 3 m1=300<br />
5 2 m1=300<br />
rank<br />
6<br />
5<br />
4<br />
3<br />
2<br />
1<br />
0<br />
sample 1 sample 2 sample 3 sample 4 sample 5<br />
f 1 f 2 f 3 f 4 f 5 f 6 f 7 f 8
Discussion<br />
2<br />
Red Mulde / March<br />
2<br />
Red Mulde / April<br />
1.5<br />
1.5<br />
1<br />
1<br />
RMU 0309<br />
RMU 0409<br />
0.5<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0<br />
200<br />
400<br />
600<br />
800<br />
0.5<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0<br />
200<br />
400<br />
600<br />
800<br />
0<br />
2<br />
1.5<br />
1<br />
0.5<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0 0.2 0.4 0.6 0.8 1<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
240<br />
0<br />
200<br />
400<br />
600<br />
800<br />
RMU 0709<br />
Red Mulde / July<br />
H/C<br />
2,5<br />
0<br />
0<br />
2<br />
Rank 1<br />
Rank 2<br />
1.5<br />
Rank 3<br />
Rank 4<br />
1<br />
0.5<br />
O/C<br />
0 1<br />
260<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0 0.2 0.4 0.6 0.8 1<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
260<br />
0<br />
200<br />
400<br />
600<br />
800<br />
RMU 0809<br />
Red Mulde / August<br />
260<br />
0<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0 0.2 0.4 0.6 0.8 1<br />
0 0.2 0.4 0.6 0.8 1
Discussion<br />
2<br />
Red Mulde / March<br />
2<br />
Red Mulde / April<br />
1,5<br />
1,5<br />
1<br />
1<br />
0,5<br />
0,5<br />
0<br />
2<br />
1,5<br />
H/C<br />
0 0,2 0,4 0,6 0,8 1<br />
Red Mulde / July<br />
0<br />
O/C<br />
2<br />
1,5<br />
0 0,2 0,4 0,6 0,8 1<br />
Red Mulde / August<br />
1<br />
1<br />
2,5<br />
0,5<br />
0,5<br />
tannins<br />
0<br />
0<br />
Rank 1<br />
Rank 2<br />
0Rank 3 0,2<br />
Rank 4<br />
0,4 0,6 0,8 1<br />
0 1<br />
0<br />
0 0,2 0,4 0,6 0,8 1
Discussion<br />
2<br />
Saubach / March<br />
2<br />
Saubach / April<br />
1.5<br />
1.5<br />
1<br />
SBA 0309<br />
1<br />
SBA 0409<br />
0.5<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0<br />
200<br />
400<br />
600<br />
800<br />
0.5<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0<br />
200<br />
400<br />
600<br />
800<br />
260<br />
260<br />
0<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0 0.2 0.4 0.6 0.8 1<br />
0 0.2 0.4 0.6 0.8 1<br />
2<br />
Saubach / July<br />
2<br />
Saubach / August<br />
1.5<br />
1.5<br />
1<br />
SBA 0709<br />
1<br />
SBA 0809<br />
0.5<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0<br />
200<br />
400<br />
600<br />
800<br />
0.5<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0<br />
200<br />
400<br />
600<br />
800<br />
260<br />
260<br />
0<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0 0.2 0.4 0.6 0.8 1<br />
0 0.2 0.4 0.6 0.8 1
Discussion<br />
2<br />
White Mulde / March<br />
2<br />
White Mulde / April<br />
1.5<br />
1.5<br />
1<br />
1<br />
WMU 0309<br />
WMU 0409<br />
0.5<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0<br />
200<br />
400<br />
600<br />
800<br />
0.5<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0<br />
200<br />
400<br />
600<br />
800<br />
260<br />
260<br />
0<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0 0.2 0.4 0.6 0.8 1<br />
0 0.2 0.4 0.6 0.8 1<br />
2<br />
White Mulde / July<br />
2<br />
White Mulde / August<br />
1.5<br />
1.5<br />
1<br />
WMU 0709<br />
1<br />
WMU 0809<br />
0.5<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0<br />
200<br />
400<br />
600<br />
800<br />
0.5<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0<br />
200<br />
400<br />
600<br />
800<br />
260<br />
260<br />
0<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0 0.2 0.4 0.6 0.8 1<br />
0 0.2 0.4 0.6 0.8 1
Discussion<br />
2<br />
Sauteich Effluent // March<br />
2<br />
Sauteich Effluent // April<br />
1.5<br />
1.5<br />
1<br />
0.5<br />
Excitation (nm)<br />
360<br />
340<br />
Excitation (nm)<br />
320<br />
300<br />
280<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0<br />
200<br />
0<br />
400<br />
200<br />
600<br />
400<br />
800<br />
600<br />
800<br />
TSP 0309<br />
STE 0309<br />
1<br />
0.5<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0<br />
200<br />
400<br />
600<br />
800<br />
TSP STE 0409<br />
260<br />
260<br />
260<br />
0<br />
240<br />
300 350 400 450 500 550<br />
240<br />
300 350 400 Emission 450(nm)<br />
500 550<br />
Emission (nm)<br />
0<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0 0.2 0.4 0.6 0.8 1<br />
0 0.2 0.4 0.6 0.8 1<br />
2<br />
Sauteich Effluent // July<br />
2<br />
Sauteich Effluent // August<br />
1.5<br />
1.5<br />
1<br />
STE TSP 0709 0709<br />
1<br />
STE TSP 0809 0809<br />
0.5<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
Excitation (nm)<br />
300<br />
280<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0 0<br />
200 200<br />
400 400<br />
600 600<br />
800 800<br />
0.5<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
Excitation (nm)<br />
300<br />
280<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0 0<br />
200 200<br />
400 400<br />
600 600<br />
800 800<br />
260<br />
260<br />
260<br />
260<br />
0<br />
240 240<br />
300 300350 350400 400450 450500 500550<br />
550<br />
Emission Emission (nm) (nm)<br />
0<br />
240 240<br />
300 300350 350400 400450 450500 500550<br />
550<br />
Emission Emission (nm) (nm)<br />
0 0.2 0.4 0.6 0.8 1<br />
0 0.2 0.4 0.6 0.8 1
2<br />
Effluent / March<br />
2<br />
Effluent / April<br />
1.5<br />
1.5<br />
1<br />
1<br />
TSP 0309<br />
TSP 0409<br />
0.5<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0<br />
200<br />
400<br />
600<br />
800<br />
0.5<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0<br />
200<br />
400<br />
600<br />
800<br />
260<br />
260<br />
0<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0 0.2 0.4 0.6 0.8 1<br />
0 0.2 0.4 0.6 0.8 1<br />
2<br />
Effluent / July<br />
2<br />
Effluent / August<br />
1.5<br />
1.5<br />
1<br />
0.5<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0<br />
200<br />
400<br />
600<br />
800<br />
TSP 0709<br />
1<br />
0.5<br />
Excitation (nm)<br />
360<br />
340<br />
320<br />
300<br />
280<br />
0<br />
200<br />
400<br />
600<br />
800<br />
TSP 0809<br />
260<br />
260<br />
0<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0<br />
240<br />
300 350 400 450 500 550<br />
Emission (nm)<br />
0 0.2 0.4 0.6 0.8 1<br />
0 0.2 0.4 0.6 0.8 1
2<br />
Discussion<br />
March<br />
Rank 1<br />
2<br />
April<br />
Rank 1<br />
1.5<br />
1.5<br />
H/C<br />
1<br />
H/C<br />
1<br />
Red Mulde<br />
Red Mulde<br />
Saubach<br />
Saubach<br />
0.5<br />
Sauteich<br />
0.5<br />
Sauteich<br />
Effluent<br />
Effluent<br />
White Mulde<br />
White Mulde<br />
0<br />
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1<br />
0<br />
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1<br />
O/C<br />
O/C<br />
2<br />
2<br />
July<br />
Rank 1<br />
August<br />
Rank 1<br />
1.5<br />
1.5<br />
H/C<br />
1<br />
H/C<br />
1<br />
Red Mulde<br />
Red Mulde<br />
Saubach<br />
Saubach<br />
0.5<br />
Sauteich<br />
0.5<br />
Sauteich<br />
Effluent<br />
Effluent<br />
White Mulde<br />
White Mulde<br />
0<br />
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1<br />
O/C<br />
0<br />
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1<br />
O/C
Discussion<br />
2<br />
Red Mulde / March<br />
2<br />
Red Mulde / April<br />
1.5<br />
1.5<br />
1<br />
1<br />
0.5<br />
0<br />
2<br />
1.5<br />
0 0.2 0.4 0.6 0.8<br />
0<br />
1<br />
Red Mulde / July<br />
2.5<br />
Rank 1<br />
0.5<br />
Rank 2<br />
Rank 3<br />
Rank 04<br />
Rank 5<br />
0 1<br />
2<br />
1.5<br />
0 0.2 0.4 0.6 0.8 1<br />
Red Mulde / August<br />
1<br />
1<br />
0.5<br />
0.5<br />
0<br />
0<br />
0 0.2 0.4 0.6 0.8 1<br />
0 0.2 0.4 0.6 0.8 1
Discussion<br />
2,5<br />
Tannic acids<br />
compositions Tanninverbindungen reported in<br />
the aus literature der Literatur<br />
2<br />
CHO<br />
1,5<br />
H/C<br />
1<br />
0,5<br />
no<br />
Tannin 1<br />
Tannin 2<br />
Tannin 3<br />
Tannin 4<br />
0<br />
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1<br />
O/C
Discussion<br />
Gallotannins (hydrolyzable)
Discussion<br />
Proanthocyanidins (condensed tannins) polymeric flavanoids
Discussion<br />
Pivot chart<br />
rank RMU<br />
Sample 1 2 3 4 total<br />
RMU3 207 97 97 237 638<br />
RMU4 96 191 228 123 638<br />
RMU7 138 199 195 106 638<br />
RMU8 217 144 115 162 638<br />
total 658 631 635 628 2552
Discussion<br />
0.4<br />
0.3<br />
AImod = (1 + C - 0.5·O - S - 0.5·H) / (C - 0.5·O - S - N)<br />
CHO<br />
SRFA<br />
TSP3<br />
TSP4<br />
TSP7<br />
TSP8<br />
number / total number<br />
0.2<br />
0.1<br />
0<br />
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9<br />
AImod<br />
1000<br />
800<br />
AImod = (1 + C - 0.5·O - S - 0.5·H) / (C - 0.5·O - S - N)<br />
CHO<br />
SRFA<br />
TSP3<br />
TSP4<br />
TSP7<br />
TSP8<br />
total number<br />
600<br />
400<br />
200<br />
0<br />
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9<br />
AImod
0.4<br />
Discussion<br />
AImod = (1 + C - 0.5·O - S - 0.5·H) / (C - 0.5·O - S - N)<br />
0.35<br />
0.3<br />
CHO<br />
RMU3<br />
WMU3<br />
SBA3<br />
STE3<br />
TSP3<br />
0.4<br />
0.35<br />
0.3<br />
AImod = (1 + C - 0.5·O - S - 0.5·H) / (C - 0.5·O - S - N)<br />
CHO<br />
RMU4<br />
WMU4<br />
SBA4<br />
STE4<br />
TSP4<br />
number / total number<br />
0.25<br />
0.2<br />
0.15<br />
number / total number<br />
0.25<br />
0.2<br />
0.15<br />
0.1<br />
0.1<br />
0.05<br />
0.05<br />
0<br />
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9<br />
0<br />
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9<br />
AImod<br />
AImod<br />
0.4<br />
0.35<br />
0.3<br />
AImod = (1 + C - 0.5·O - S - 0.5·H) / (C - 0.5·O - S - N)<br />
CHO<br />
RMU7<br />
WMU7<br />
SBA7<br />
STE7<br />
TSP7<br />
0.4<br />
0.35<br />
0.3<br />
AImod = (1 + C - 0.5·O - S - 0.5·H) / (C - 0.5·O - S - N)<br />
CHO<br />
RMU8<br />
WMU8<br />
SBA8<br />
STE8<br />
TSP8<br />
number / total number<br />
0.25<br />
0.2<br />
0.15<br />
number / total number<br />
0.25<br />
0.2<br />
0.15<br />
0.1<br />
0.1<br />
0.05<br />
0.05<br />
0<br />
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9<br />
0<br />
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9<br />
AImod<br />
AImod
2<br />
Discussion<br />
Rank 5<br />
CHO<br />
SRFA C < 21<br />
2<br />
Rank 5<br />
CHO<br />
SRFA C > 20<br />
1.5<br />
Rank 4<br />
1.5<br />
Rank 4<br />
Rank 3<br />
Rank 3<br />
Rank 2<br />
Rank 2<br />
H/C<br />
1<br />
Rank 1<br />
H/C<br />
1<br />
Rank 1<br />
H/C<br />
0.5<br />
Data from<br />
Koch, B.P. et al. (2007)<br />
0<br />
Anal. Chem. 79, 1758<br />
2<br />
1.5<br />
1<br />
0 0.2 0.4 0.6 0.8 1<br />
O/C<br />
Rank 5<br />
Rank 4<br />
Rank 3<br />
Rank 2<br />
Rank 1<br />
CHO<br />
RMU7 C < 21<br />
H/C<br />
0.5<br />
Suwannee River Fulvic Acid<br />
0<br />
2<br />
1.5<br />
1<br />
0 0.2 0.4 0.6 0.8 1<br />
Rank 5<br />
Rank 4<br />
Rank 3<br />
Rank 2<br />
Rank 1<br />
O/C<br />
CHO<br />
RMU7 C > 20<br />
0.5<br />
0<br />
0<br />
0 0.2 0.4 0.6 0.8 1<br />
0 0.2 0.4 0.6 0.8 1<br />
O/C<br />
O/C<br />
0.5<br />
Red Mulde / July
2.5<br />
2<br />
H/C<br />
1.5<br />
1<br />
0.5<br />
0<br />
CHON1 CHOS1 CHON2-6<br />
0 0.2 0.4 0.6 0.8 1<br />
O/C